KR960010009B1 - Non-photographic method for patterning organic polymer films - Google Patents

Abstract

No summary

Description

Non-Photographic Method of Patterning Organic Polymer Film

The figure consists of two figures.

1 is a schematic of the method of the invention in a negative mode of action.

2 is a schematic of the method of the invention in a positive mode of action.

Field of invention

The present invention relates to a non-photographic method of patterning organic polymer films, in particular organic polymer films for use in the production of monolayer and multilayer electronic devices such as thick film hybrids.

Background of the Invention

Thick film methods have historically been of interest as a method of making stringent and reliable conductors, dielectrics and resistors. This thick film method is suitable for economic production with short production runs. The ability to pattern multilayer structures has made it possible to fabricate devices with extremely high density circuits. In a multilayer structure, the continuous levels of conductors are separated by insulating dielectric layers and interconnected by vias through the dielectric layers.

Multilayer methods are less economical than single layer methods because they require careful inspection, interlayer realignment, and careful processing to prevent blistering and cracking.

The most reliable solution to the above problems with multilayer products is to reduce the number of layers in a given structure by reducing the line and space dimensions. However, this method has a problem in that the resolution is limited by limiting the size of the via used to connect the layers of the circuit to a thickness of about 0.025 to about 0.038 cm (10 to 15 mils) in the thick film screen printing method. Likewise, conductors are limited to very narrow linewidths and spaces of about 0.013 to about 0.018 cm (5 to 7 mil) lines and spaces in production.

In addition, many other methods have been studied for obtaining finer pitch lines and smaller vias. The extremely fine screen mesh and the improved emulsion backing made it possible to obtain a limited product with line resolution as low as about 0.010 cm (4 mil) line / space. Photoformable pastes have been developed to allow vias to be less than about 0.013 cm (5 mils) and line / space pitches from about 0.005 to about 0.008 cm (2 to 3 mils). Further, the thick film metallization was patterned with a photoresist and etched to produce fine line patterns, and the thin film conductors were plated to produce fine line patterns having high conductivity.

However, all of these methods have drawbacks. For example, fine mesh screens typically discard thinner conductors and dielectric layers than required. The photoformable paste has a large amount of organic material that can produce dirty combustion products that double the shrinkage during firing and render the plastic parts unusable. Conductors made using photoformable pastes have unnecessary edge curls, which can reduce the reliability of circuits made of photoformable pastes. In addition, any photolithography method that requires etch, photoresist, or plating is lengthy, process sensitive, and uneconomical.

Summary of the Invention

Therefore, the present invention relates to a non-photographic method of forming a pattern on an organic polymer film, which method comprises: a. Applying to the substrate an unpatterned first layer consisting of a solid organic polymer that can be dispersed in a predetermined eluent, b. Applying to the unpatterned first layer a patterned second layer comprising a formulation capable of varying the dispersibility of the solid organic polymer in a predetermined eluent, c. Patterning diffusion of a dispersibility-changing agent into the underlying solid first layer, and d. The area of the lower first layer that can be dispersed in the eluent consists of a continuous step of washing and removing with a predetermined eluent.

The present invention can be used to produce negative images or positive images.

In the negative-acting mode, the method is a. Applying an unpatterned first solid organic polymer layer consisting of a solid organic polymer to a substrate, b. A patterning consisting of a solid organic polymer in the unpatterned first layer, (1) a dispersant for the polymer of the first organic polymer layer and (2) a dispersibility modifier having an atmospheric boiling point higher than the solvent and optionally a viscous dispersion of the solvent. Applying a second layer, c. Drying the patterned second layer to remove the solvent therefrom, and patterning diffusion of the dispersibility modifier into the lower first organic polymer layer, and d. A continuous step of washing and removing the diffusion patterned region of the patterned second layer and the lower first layer in an eluent that can be dispersed by the diffusion patterned region of the second layer and the first layer.

In a positive-acting mode, the method comprises: a. Applying to the substrate an unpatterned first layer consisting of a solid organic polymer that can be dispersed in a predetermined solvent, b. Applying to the unpatterned first layer a patterned second layer comprising a dispersibility modifier capable of reducing the dispersibility of the organic polymer in a solvent, c. Heating the patterned second layer to patterned diffuse the dispersibility modifier into the lower first organic polymer layer and reduce the dispersibility of the diffusion patterned region of the first layer polymer in a solvent, and d. The unpatterned region of the lower first layer consists of a sequential step of washing away in a predetermined solvent.

Detailed description of the drawings

In Figure 1, schematically a. Applying an unpatterned first solid organic polymer layer (3) to the substrate (1), b. A solution of a solubilizer and a solvent which is soluble in the solid organic polymer in the unpatterned first solid organic polymer layer (3), (a) in the polymer of the first organic polymer layer (3), and (b) has an atmospheric boiling point higher than that of the solvent. Applying a patterned second layer 5 consisting of, c. Heating the patterned second layer 5 to remove solvent therefrom and patterning diffusion of the solubilizer into the lower first solid organic polymer layer 3a, and d. The diffusion patterning region 3a of the patterned second layer 5 and the lower first solid organic polymer layer is dissolved in the solid phase organic polymer of the second layer 5 and the diffusion patterning layer of the first layer 3. A negative functional non-photographic method of forming a pattern in an organic polymer film, consisting of a continuous step of washing and removing in a second solvent which can be employed.

In Figure 2, schematically a. Applying to the substrate 11 an unpatterned first layer 13 consisting of a soluble solid organic polymer in a predetermined solvent, b. Applying to the unpatterned first layer (13) a patterned second layer (15) consisting of a desolubilizing agent which can reduce the solubility of the organic polymer in the solvent and is essentially insoluble in the solvent. c. The patterned second layer 15 is heated to pattern-diffuse the insolubilizer into the lower first organic polymer layer 13 and insoluble in the solvent in the diffusion patterned region 13a of the polymer in the first layer. Giving, d. A positive functional non-photographic method of forming a pattern in an organic polymer film, consisting of a continuous step of washing and removing the unpatterned region of the lower first layer 13 in a predetermined solvent.

If the insolubilizer depletion regions of the patterned second layer 15 are soluble in the solvent, these regions are removed during the solvent wash step. On the other hand, if the insolubilizer depletion regions of the patterned second layer 15 are insoluble in the solvent, these regions will remain after the solvent wash step.

Justice

As used herein, the following terms have the following meanings.

The term eluent means any liquid or gaseous fluid that can be transformed into a form that can dissolve or otherwise disperse the lower unpatterned layer.

The term dispersible means that in relation to a film of a certain substance, this substance can be replaced or removed by the physical or chemical action of the cleaning liquid or by lifting off.

The term volatile solvent means any solvent that can be removed by evaporation at a temperature of 120 ° C. or below, 1 atmosphere.

Removal of the diffusion patterning region of the lower polymer layer may occur by a series of mechanisms: (1) a mechanism for dissolving the polymer in the diffusion patterning region in a solvent and thus washing the resulting polymer solution; (2) a mechanism for decomposing the polymer in the diffusion patterning region and washing and / or evaporating the decomposition product; (3) a mechanism for emulsifying the polymer in the diffusion patterning region with a detergent and removing the dispersion with an aqueous washing solution; (4) a mechanism for softening the polymer in the diffusion patterning region by a solvent and / or plasticizing action to reduce its adhesion to the substrate and to peel the softened film from the substrate; (5) a mechanism for ionizing the polymer in the diffusion patterning region and washing the ionizing polymer from the substrate with an ionic aqueous solution; And (6) a mechanism for insolubilizing the polymer in the diffusion patterning region and removing a polymer film other than the diffusion patterning region.

Detailed description of the invention

A. Substrate

The method of the present invention is carried out on an inorganic substrate such as Al ₂ O ₃ , SiO ₂ , silicon, AlN, or an organic substrate such as polyimide, phenoxy resin, epoxy resin, or a composite substrate filled with an organic polymer. Can be used.

B. Organic Polymer

As long as the solid organic polymer is substantially amorphous and has adequate solubility properties by itself or by the addition of solubilizers or insolubilizers, various solid organic polymers can be used as materials for either or both of the polymer layers.

An essential property of both polymer layers is that the polymer should be substantially amorphous. Therefore, as used herein, the term amorphous polymer means a polymer having a crystallinity of about 50% or less. Such virtual amorphousness is essential to facilitate diffusion of the solubility modifier from the patterned second layer (upper polymer layer) to the lower polymer layer. Accordingly, among the many types of amorphous polymers that can be used in the process of the present invention, the following are particularly preferred.

I. By polymerization method

Addition polymer

Condensation polymer

II. By physical characteristics

Hydrolyzable polymer

Crosslinkable polymer

Thermoplastic polymer

Ionizable polymer

Thermosetting polymer

Elastomer

III. By composition

Polycarbonate

Polyimide

Polyester

Olefin Copolymer

Polyacrylates (including methacrylates)

polystyrene

Phenoxy resin

Phenolic-Formaldehyde Resin

Cellulose polymer

Poly (vinyl acetate)

Poly (vinyl butyral)

Poly (vinyl chloride)

Poly (vinyl chloride acetate)

C. Formulation and Application

The method of the present invention has been developed primarily for the purpose of use for smaller thickness layers, for example layers used in the manufacture of electronic components. Typically, the second layer polymer has a thickness in the range of 10 to 30 microns while the first layer polymer can have a much larger thickness in the range of 10 to 100 microns. The thickness of the patterned layer is mainly limited by the method of use rather than by consideration of operability.

The amount of solubilizer in the second layer should be such that the solubilizer can be sufficiently provided to the lower first layer by diffusion. Thus, the second layer should contain at least 10% by weight or more of a solubilizer, and may contain as much as 90% by weight, depending on the solubility relationship of each polymer.

Also, in some cases, it is desirable to add a plasticizer or other solubilizer to the lower first layer so that the polymer can be more sensitive to the action of the solubilizer diffused from the second polymer layer.

In general, the individual component layer manufacturing steps by the method of the present invention are similar to the manufacturing methods of conventional thick film, green tape and polymer techniques known to those skilled in the art. Therefore, although the process is not a new method as follows, the preferable method of compounding and manufacturing the material to be used in the present invention will be described.

1. Paste Manufacturing Process and Dielectric Underprint

a. Premilling: The dielectric inorganic component was pre-dispersed by rolling in a ball mill with almost equal weight of methanol or isopropanol for 30-90 minutes, then decanted and left for 2-16 hours to precipitate solids. The symbolic alcohol is then decanted and the solid is dried under nitrogen to reduce the possibility of explosion at room temperature and completely dried in the oven for 1 hour.

b. Vehicle Preparation: Solvent, resin, antioxidant and t-butylanthraquinone are all added together to the resin bottle and heated to dissolve. If necessary, a humectant may be added to the solution prior to paste preparation. The resins and solvents show the best function in these pastes when they are heated with the paste to a maximum of 140 ° C. and then cooled to 70 ° C. suitable for the addition of ionol, t-butylanthraquinone and optionally a humectant. In addition, the humectant may be added at the next paste preparation step.

c. Paste Preparation: Pastes are prepared by uniformly mixing the predispersed solid with the vehicle and other organic components, and then rolling milling until an acceptable polishing gauge (at least about 12/8) is obtained. If desired, some small amount of vehicle and / or solvent is retained in the formulation before roll milling, and then a sufficient amount of vehicle and / or solvent is added after roll milling to achieve the desired viscosity. Thus, the solvent or resin may be present in the final formulation in amounts slightly or less than the prescribed amounts described in the formulation amounts.

In addition, the amount of plasticizer required for the optimization of function may vary slightly depending on the lot of paste, so that a small amount of plasticizer may be retained in the formulation before roll milling. In the actual manufacturing process, several test formulations are made at the main plant equipment to determine the best formulation for a particular combination of vehicle and inorganic solids.

2. Conductor Underprint

a. Vehicle Manufacturing: This vehicle is manufactured exactly as the vehicle for dielectric underprint.

b. Paste Preparation: The conductor inorganic components are uniformly mixed with the vehicle and the other organic components described above. This mixture is then roll milled to obtain an acceptable polishing gauge (about 15/8 or more). Some of the solvent, vehicle and / or plasticizer may be retained prior to roll milling to optimize the amount of these components later. Milling and blending methods are similar to those used for dielectrics.

3. Pattern Overprint

Vehicle Preparation: A vehicle is prepared by dissolving ethyl cellulose resin in a solution of a plasticizer and a solvent at elevated temperature in advance, which facilitates mixing of the components in paste formulation. Solvents and / or plasticizers in the final formulation are not used at all to prepare the vehicle because some of the solvent and / or plasticizer can be added after roll milling as needed to optimize their amount in the final formulation. Thus, the final blend may not necessarily correspond to the blend amounts set forth herein. However, the pastes produced exhibit some variability.

4. Paste Manufacturing and Printing

The inorganic and organic components of the pattern forming paste not contained in the vehicle are mixed uniformly with the vehicle described above. This mixture is then roll milled to an acceptable polishing gauge (about 15/8 or more). Some of the solvent, vehicle, and / or plasticizer may be withheld prior to roll milling so that the amount of these components can be utilized most effectively later. Milling and blending methods are similar to those used for dielectrics.

Typically, the dielectric paste is printed twice at a speed of about 2.54 to about 5.08 cm / sec (1 to 2 inches / sec) rubber roller using a 200 mesh screen. The pattern forming paste is printed on the dielectric at a faster speed because only a small portion of the screen is an open mesh.

The conductor paste is printed on a 325 or 400 mesh screen depending on the desired conductor thickness and resolution. Similarly, the pattern forming paste prints on a 325 or 400 mesh screen that can most effectively utilize the amount of plasticizer delivered to the underprint. Coarser screens and fewer prints are more needed for dielectrics because thin films are typically used as conductors.

5. Patterning of Selected Materials

One of the advantages of the diffusion patterning method of the present invention is that it is possible to pattern a relatively thick underprint pattern with a thin pattern forming film. For example, when the thickness of a pattern forming agent such as butyl benzine phthalate is set to 1, the in-print of 5 to 10 materials having the thickness can be patterned using this pattern forming agent. Therefore, this method can be used to make a pattern of very accurate thickness. For example, to form the same thickness as the composition of Example 1 by screen printing, about 75 to 175 microns (3 to 7 mils) of correctly registered thick film ink must be deposited, during which the via openings are approximately from the inlet. Maintain a small via opening as small as 0.010 cm (4 mil).

This ability to pattern very thick layers using relatively thin prints has led to other pattern formation methods that have significantly greater processing capacity advantages over screen printing methods. In addition to the screen printing method, the material of Example 1 is used to generate the pattern by a flexoraphic patterning process in which the ink for pattern formation is transferred from the printing plate to the dielectric underprint, and then diffused and developed. Proved. The possible processing power of the flexure application is significantly greater than that of the screen printing method. If the screen printing method can process about 2.58 to about 3.23 m <2> (4,000-5,000 in <2>) per hour typically, it is thought that the processing capacity is high. The flexure system or offset system can achieve diffusion patterning of about 3.87 to about 12.90 m 2 (6,000 to 20,000 in 2) per minute with sharper resolution.

Other application methods of the pattern forming print include (1) a method of manufacturing a circular circuit board without writing an artwork or exposing the substrate by directly writing on a plotter with a pen, and (2) a commercial computer printer. Writing with an ink jet printhead similar to that seen in (3), and (3) solid solubility of compatible plasticizers, resins, acids or bases, such as compatible on an underprint, such as by a laser printer. There is a method using a variable agent.

In order to take full advantage of the processing power advantages of the present invention, the method of underprinting is other than screen printing. It is preferred to apply in the same manner as for example in the form of cast tapes. The development of the patterned part must be carried out in a batch process in order to maintain the processing capacity of the remainder of the system equally, and the batch process must also be fired in a large kiln to control the production scale. Thus, those skilled in the polymer art will recognize that each polymer species is compatible with many different types of plasticizers or nonvolatile solvents. As a result, there are a myriad of suitable combinations of polymers / solvents / nonsolvents. The commercially available polymers and plasticizers and solvent / nonsolvent systems of the examples listed below can be used to practice the present invention.

D. Polymer / Plastic Combination for Diffusion of Patterning

1. Cellulose Acetate

Compatible plasticizers include triethyl citrate, acetyl triethyl citrate, epoxy type plasticizers, glycerol acetates (mono, di, tri), dimethyl adipate, tridecyl adipate, di-n-hexyl azelate, ethylene glycol diacetate , Diethylene glycol esters and derivatives, triethylene glycol esters (eg methyl, ethyl, propyl, butyl), di- and tripropylene glycol esters. In addition, long chain hydrocarbons and aromatic hydrocarbons, chlorinated paraffins, tricresyl phosphates, alkyl phthalates (dimethyl to dibutyl), dimethyl sebacate and sulfonic acid sold by Dover Chemical Co., New York, NY Derivatives such as o- and p-toluene sulfonamides are also compatible plasticizers.

2. Cellulose Acetate Butyrate

Compatible plasticizers include citric acid esters (ethyl to butyl), acetyl epoxy stearate, glycerol di- and triacetates, dimethyl and dibutyl adipate, tridecyl adipate, dihexyl adipate, diethylene glycol dipellagonate, di Propylene glycol caprylate and heptanoate, hydrocarbons, sucrose acetate isobutyrate, dioctyl isophthalate, glycerol monolaurate, trioctyl trimellitate, triisodecyl trimellitate, isopropyl myristate, n-butyl myriline States, butyl oleate, tetrahydrofurfuryl oleate, chlorinated paraffins and derivatives, diethylene glycol dipellagonate, alkyl phosphates (triethyl to tributyl), triphenyl phosphate, tricresyl phosphate, triisopropyl phenyl phosphate, Trixylenyl For Pate, phthalic esters (dimethyl to dihexyl), mixed alcohol phthalates (e.g. butyl benzyl phthalate, butylethylhexyl phthalate and dicyclohexyl phthalate), various polyesters, methyl ricinoleate, dimethyl sebacate, many stearic acid derivatives (Eg, alkyl (propyl to octyl) stearate, 1,2-propylene glycol monostearate) and dioctyl terephthalate.

3. Cellulose Nitrate

Cellulose nitrate is exceptionally compatible with so many various plasticizers. Some of the plasticizers include acid esters of methyl abietin (methyl abietate), acetic acid esters (cumphenyl acetate), adipic acid derivatives (e.g. benzyloctyl adipate, diisodecyl adipate, tridecyl adipate), Azelaic acid esters (e.g. diisooctyl azelate), diethylene glycol dibenzoate), triethylene glycol dibenzoate, citrate (e.g. triethyl citrate), epoxy plasticizers, polyvinyl methyl ether, glycerol mono Di- and triacetates, ethylene glycol diacetates, polyethylene glycols 200-1000, phthalate esters (dimethyl to dibutyl), isophthalic esters (dimethyl, diisooctyl, di-2-ethylhexyl), melitates (e.g. , Trioctyl trimellitate, isooctylisodecyl trimellitate), isopropyl myristate, methyl and propyl oleate, isopropyl And isooctyl palmitate, chlorinated paraffins, phosphoric acid derivatives (eg triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl phosphate), polyesters, dibutyl sebacate, dioctyl sebacate, stearates (eg , Octyl stearate, butoxyethyl stearate, tetramethylene glycol monostearate), sucrose derivatives (eg sucrose octoacetate), sulfonic acid derivatives (eg benzenesulfonmethylamide) or dioctyl terephthalate.

4. Ethyl Cellulose

Most plasticizers that are compatible with cellulose nitrate are also compatible with ethyl cellulose. Thus, ethyl cellulose is compatible with many plasticizers. Some of the plasticizers include acid esters of methyl abietin (methyl abietate), acetic acid esters (cumphenyl acetate), adipic acid derivatives (e.g. benzyloctyl adipate, diisodecyl adipate, tridecyl adipate), Azelaic acid esters (e.g. diisooctyl azelate), diethylene glycol dibenzoate, triethylene glycol dibenzoate, citrate (e.g. triethyl citrate), epoxy plasticizers, polyvinyl methyl ether, glycerol mono- , Di- and triacetates, ethylene glycol diacetates, polyethylene glycol 200-1000, phthalate esters (dimethyl to dibutyl), isophthalic acid esters (dimethyl, diisooctyl, di-2-ethylhexyl), melitates (e.g. Trioctyl trimellitate, isooctylisodecyl trimellitate), isopropyl myristate, methyl and propyl oleate, isopropyl Isooctyl palmitate, chlorinated paraffin, phosphoric acid derivatives (e.g. triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, triphenyl phosphate), polyesters, dibutyl sebacate and dioctyl sebacate, stearates (e.g. Octyl stearate, butoxyethyl stearate, tetramethylene glycol monostearate), sucrose derivatives (eg sucrose octoacetate), sulfonic acid derivatives (eg benzenesulfonmethylamide) or dioctyl terephthalate.

5. Polystyrene

Typical plasticizers include methyl abietate, hydrogenated methyl abietate, benzyloctyl adipate, a plurality of alkyl adipates (butyl to decyl and mixed esters); Azelaic acid esters such as di- (2-ethylhexyl) azelate; Some benzoic acid esters such as diethylene glycol dibenzoate; Citric acid derivatives such as tri-n-butyl citrate; Oleic acid esters such as methyl oleate; Chlorinated paraffin; Alkyl and aryl phosphates such as tributyl phosphate and tricleyl phosphate; Various phthalate esters such as dimethyl, dipropyl, dibutyl or dioctyl phthalate, butyl benzyl phthalate and other mixed alkyl and aryl phthalates; Ricinoleic acid and sebacic acid ester; some stearate esters such as n-butyl stearate; Poly alpha methyl styrene; And dioctyl terephthalate.

6. Poly (vinyl acetate)

Plasticizers include sulfonic acid derivatives such as o- and p-toluene sulfonamides; Sucrose derivatives such as sucrose octoacetate; Some stearates such as glycerol triacetoxy stearate; Dibenzyl sebacate; Ricinoleic acid ester; Polyester; Some phthalate esters such as dibutyl and butyl benzyl phthalate; Most phosphoric acid esters such as tributyl or triphenylphosphate; Most chlorinated paraffins; Glyceryl monooleate; Di-n-butyl maleate; Some glycol derivatives such as polyethylene glycol, di- (2-ethylhexate) and citric acid esters such as triethyl or tri-n-butyl citrate.

7. Poly (vinyl Butyral)

Methyl abietate, cumphenyl acetate, dibutyl adipate, di- (2-ethylhexyl) adipate; Tridecyl adipate, diethylene glycol diadipate, polyethylene glycol (200) dibenzoate, hydrogenated terphenyl; Citric acid alkyl esters such as triethyl citrate, tri-n-butyl citrate and triethyl citrate; Epoxidized soybean oil; Epoxidized delate esters; Cumfetyl benzyl ether; Dipropylene glycol dicaprylate; Triethylene glycol tripellagonate; Few hydrocarbon type plasticizers; Diisooctyl isophthalate; Glycerol monolaurate; Triisononyl melittate; n-propyl oleate; Glycerol monooleate; Multiple chlorinated paraffins; Pentaerythritol tetraisopentanoateheptanoate; Many phosphate esters such as alkyl phosphate (tributyl, tri-2-ethylhexyl, triphenyl and the like), tris (chloropropyl) phosphate, diphenyl octyl phosphate, diphenyl xenyl phosphate, phenyl isopropyl phenyl phosphate; Furthermore, many phthalate esters, such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicapryl phthalate, mixed phthalate, ditridecyl phthalate; Furthermore, polyester, such as a ricinoleic acid ester, such as some methyl acetyl ricinoleate, and a stearic acid ester, such as glycerol tri-acetoxy stearate; And o- and p-toluene-ethylsulfonamides.

8. Poly (vinyl chloride)

Methyl abietate, cumphenyl acetate, dibutyl adipate, di- (2-ethylhexyl) adipate; Tridecyl adipate; Diethylene glycol diadipate; Polyethylene glycol (200) dibenzoate; Hydrogenated terphenyl; Citric acid alkyl esters such as triethyl citrate, tri-n-butyl citrate and triethyl citrate, epoxidized soybean oil; Epoxidized delate esters; Cumphenyl benzyl ether; Dipropylene glycol dicaprylate; Triethylene glycol tripellagonate; Few hydrocarbon type plasticizers; Diisooctyl isophthalate; Glycerol monolaurate; Triisononyl melittate; n-propyl oleate; Glycerol monooleate; Multiple chlorinated paraffins; Pentaerythritol tetraisopentanoateheptanoate; Many phosphate esters such as alkyl phosphate (tributyl, tri-2-ethylhexyl, triphenyl, etc.), tris (chloropropyl) phosphate, diphenyl octyl phosphate, diphenyl-xylenyl phosphate, phenyl isopropyl phenyl phosphate; In addition, many phthalate esters such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicaryl phthalate, mixed phthalate, ditridecyl phthalate; In addition, polyester; Some ricinoleic acid esters such as methyl acetyl ricinoleate; Stearic acid esters such as glycerol tri-acetoxy stearate; In addition, many other epoxy plasticizers; Also, polyethylene glycol di- (2-ethylhexate); Dibutyl sebacate; Dioctyl- and dinonyl sebacate; And dioctyl terephthalate are also suitable plasticizers.

9. Vinyl Chloride / Vinyl Acetate Copolymer

Methyl abietate, cumphenyl acetate, dibutyl adipate, di- (2-ethylhexyl) adipate; Tridecyl adipate; Diethylene glycol diadipate; Polyethylene glycol (200) dibenzoate; Hydrogenated terphenyl; Citric acid alkyl esters such as triethyl citrate, tri-n-butyl citrate and triethyl citrate; Epoxidized soybean oil; Epoxidized delate esters; Cumphenyl benzyl ether; Dipropylene glycol dicaprylate; Triethylene glycol tripellagonate; Few hydrocarbon type plasticizers; Diisooctyl isophthalate; Glycerol monolaurate; Triisononyl melittate; n-propyl oleate; Glycerol monooleate; Multiple chlorinated paraffins; Penta editoritol tetraisopentanoateheptanoate; Many phosphate esters such as alkyl phosphates (tributyl, tri-2-ethylhexyl, triphenyl, etc.), tris (chloropropyl) phosphate, diphenol octyl phosphate, diphenyl-xylenyl phosphate, phenyl isopropyl phenyl phosphate, In addition, many phthalate esters such as dimethyl, diethyl, dipropyl, dibutyl, butyl benzyl, dioctyl or dicapryl phthalate, mixed phthalate, ditridecyl phthalate; In addition, polyester; Some ricinoleic acid esters such as methyl acetyl ricinoleate; Stearic acid esters such as glycerol tri-acetoxy stearate; In addition, many other epoxy plasticizers; Also, polyethylene glycol di- (2-ethylhexate); Dibutyl sebacate; Dioctyl- and dinonyl sebacate; And dioctyl terephthalate are also suitable plasticizers.

10. Polymethylmethacrylate

Compatible plasticizers include methyl abietate, camphor, cumphenyl acetate, octyl and nonyl adipate, dipropylene glycol dibenzoate, polyethylene glycol (200) dibenzoate, pentaerythritol tetrabenzoate, di- and triethylene Glycol esters, some hydrocarbon type plasticizers; Melitric acid esters such as triisononyl trimellitate; Isopropyl myristate; Isopropyl oleate; Ethylene glycol monobutyl ether oleate; Chlorinated paraffins; Phosphoric acid esters such as triethyl and tributyl phosphate, t-butyl diphenyl phosphate, tricresyl phosphate and alkyl aryl phosphate; Many phthalic acid esters such as dibutyl, dipropyl or dihexyl phthalate; Butyl benzyl phthalate; Dioctyl phthalate; Dodecyl phthalate, or dodecylhexyl phthalate; In addition, dibutyl or dioctyl sebacate; Other sebacic acid esters; Sucrose benzoate; And terephthalic acid esters such as dioctyl terephthalate. Camphor is also a useful plasticizer.

E. Solvent / Non-solvent System for Diffusion Patterning

1. Cellulose Acetate

Solvent:

Methylene chlorite / methanol, chloroformol / methanol, benzyl alcohol, phenol, ethylene glycol ether, dioxane, diethanolamine, pyridine, aniline, acetone, cyclohexanone, formic acid, acetic acid, methyl acetate, ethyl acetate / nitrobenzene, Glycol monoethyl ether acetate, nitromethane.

Non-sold:

Hydrocarbons, aliphatic ethers, weak inorganic acids.

2. Cellulose Acetate Butyrate

Solvent:

Benzene, toluene (high temperature), chloroform, carbon tetrachlorite, tetrachloroethane, methanol (high temperature), acetone, cyclohexanone, dioxane, aliphatic ester, nitroethane.

Non-sold:

Aliphatic hydrocarbons, methanol (cold), ethanol, diethyl ether.

3. Cellulose Nitrate

Solvent: (N represents nitrogen content)

N> 10.5 and <12%:

Alcohol (lower), alcohol / diethyl ether, acetone, amyl acetate, ethylene glycol ether, acetic acid (glacial acetic acid).

N≥12%:

Hydrogenated hydrocarbons, ethanol / diethyl ether, acetone, methyl amyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl butyrate, ethyl lactate, ethylene glycol ether acetate, ethylene carbonate, furan derivatives, nitrobenzene.

Non-sold:

N> 10.5 and <12%:

Higher alcohols, higher carboxylic acids, higher ketones, tricresyl phosphate.

N≥12%:

Aliphatic hydrocarbons, aromatic hydrocarbons, lower alcohols, higher alcohols (swelling), ethylene glycol, diethyl ether, dilute carboxylic acid, water.

4. Ethyl Cellulose

Solvent: (D.S. represents the degree of substitution by ethoxyl group)

D.S. = 1.0 to 1.5:

Pyridine, formic acid, acetic acid, water (cold temperature).

D.S. = 2

Methylene chlorite, chloroform, dichloroethylene, chlorohydrin, ethanol, THF.

D.S. = 2.3

Benzene, toluene, alkyl halides, alcohols, furan derivatives, ketones, acetic esters, carbon disulfides, nitromethane.

D.S. = 3.0

Benzene, toluene, methylene chloride, alcohols, esters.

Non-sold:

D.S. = 1.0 to 1.5:

ethanol.

D.S. = 2.0

Hydrocarbons, carbon tetrachlorite, trichloroethylene, alcohols, diethyl ether, ketones, esters, water.

D.S. = 2.3

Ethylene glycol, acetone (cold temperature).

D.S. = 3.0

Hydrocarbons, decalin, xylene, carbon tetrachloride, tetrahydrofurfuryl alcohol, diols, n-propyl ethers.

5. Polystyrene

Solvent:

Cyclohexane (> 35 ° C), cyclohexane / acetone, methylcyclohexane / acetone, decahydronaphthalene / diethyl oxalate, benzene, toluene, ethylbenzene, styrene, lower chlorinated aliphatic hydrocarbons, phenol / acetone, THF, dimethyl tetra Hydrofuran, dioxane, methyl ethyl ketone, diisopropyl ketone, cyclohexanone, glycol formal, ethyl acetate, butyl acetate, methyl-, ethyl-, n-butyl phthalate, 1-nitropropane, carbon disulfide, tri Butyl phosphate, phosphorus trichloride.

Non-sold:

Saturated hydrocarbon, alcohol, phenol, diol, ethylene chlorohydrin, perfluorobenzene, 1,2,3,4-tetrafluorobenzene (<10 ° C), diethyl ether, glycol ether, acetone, acetic acid, isobutyl Phthalate, methylhexyl phthalate, tri (chloroethyl) phosphate, tricresyl phosphate.

6. Poly (vinyl acetate)

Solvent:

Benzene, toluene, chloroform, carbon tetrachloride / ethanol, dichloroethylene, ethanol (20:80), chlorobenzene, methanol, ethanol / water, n-butanol / water, allyl alcohol, 2,4-dimethyl-3-pentanol Benzyl alcohol, tetrahydrofurfuryl alcohol, THF, dimethyltetrahydrofuran, dioxane, glycol ether, glycol ether ester, acetone, methyl ethyl ketone, acetic acid, lower aliphatic ester, vinyl acetate, acetal, acetonitrile, nitromethane, DMF, DMSO, Chloroform, Kellobenzene.

Non-solvent: (sw represents swelling)

Saturated hydrocarbon, xylene (sw), mesitylene, carbon tetrachloride (sw), ethanol (anhydrous, sw), anhydrous alcohol C> 1, ethylene glycol, cyclohexanol, methylcyclohexanol, diethyl ether (anhydrous, alcohol free ), Higher ester C> 5, carbon disulfide, water (sw), dilute acid, dilute alkali.

7. Poly (vinyl butyral)

Solvent:

Acetalization 70%:

Alcohols, cyclohexanone, ethyl lactate, ethylene glycol acetate.

Acetalization 77%:

Methylene chloride, alcohol, acetone, methyl ethyl ketone, cyclohexanone, lower ester, methylene chloride, alcohol, ketone, lower ester.

Acetalization 83%:

Methylene chloride, alcohols, ketones, lower esters.

Non-sold:

Acetalization 70%:

Aliphatic, cycloaliphatic and aromatic hydrocarbons (sw), methylene chloride, aliphatic ketones, most esters, water.

Acetalization 77%:

Aliphatic, cycloaliphatic and aromatic hydrocarbons (sw), methyl isobutyl ketone, higher esters.

Acetalization 83%:

Aliphatic, cycloaliphatic and aromatic hydrocarbons (sw), methanol, higher esters.

8. Poly (vinyl chloride)

Solvent:

High molecular weight:

THF, acetone / carbon disulfide, methyl ethyl ketone, cyclopentanone, cyclohexanone, DMF, nitrobenzene, DMSO.

Low molecular weight:

Toluene, xylene, methylene chloride, ethylene chloride, perchloro ethylene / acetone, 1,2-dichlorobenzene, dioxane, acetone / carbon disulfide, cyclopentanone, cyclohexanone, diisopropylketone, mesityl oxide, iso Poron, DMF, nitrobenzene, HMPT, tricresyl phosphate.

Chlorination, 63% Cl:

Aromatic hydrocarbons, chloroform, chlorobenzene, THF, dioxane, acetone, cyclohexanone, butyl acetate, nitrobenzene, DMF, DMSO.

Non-sold:

All molecular weights:

Aliphatic hydrocarbon, mineral oil, aromatic hydrocarbon (sw), vinyl chloride, alcohol, glycol, aniline (sw), acetone (sw), carboxylic acid, acetic anhydride (sw), ester, nitroparaffin (sw), carbon disulfide, Non-oxidizing acid, alkali.

Chlorination, 63%:

Aliphatic and cycloaliphatic hydrocarbons, carbon tetrachloride, methyl acetate, nitromethane, organic and inorganic acids.

9. Vinyl Chloride / Vinyl Acetate Copolymer

Solvent:

Chloroform, chlorobenzene, pyridine, dioxane, cyclohexanone, ethyl acetate.

Non-sold:

Benzene, alcohol, diethyl ether, water.

10. Polymethylmethacrylate

Solvent:

Dimethyl formamide, methylene chloride, chloroform, ethylene dichloride, trichloroethylene, chlorobenzene, methyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, butyl lactate, cellosolve acetate, 1,4-dioxane , Tetrahydrofuran, benzene, acetone, methyl ethyl ketone, acetonitrile, nitromethane, nitroethane, 2-nitropropane, toluene, diacetone alcohol.

Non-sold:

Methyl, ethyl, propyl, amyl alcohol; Cyclohexanol; Ethanol glycol; Glycerol; In addition, formamide, carbon tetrachloride; Diethyl and diisopropyl ethers; FREON MF and TF; Hexane, cyclohexane, mineral spirits; Turpentin; Diisobutyl ketone; Cyclohexanone, isophorone; Castor oil; Linseed oil; Trichloroethane.

Example 1

Two kinds of pastes, one of which is a dielectric paste and the other of which is a pattern forming paste, are combined and produced as follows.

Glass A has a D ₅₀ of about 4 to 4.5 microns, which is milled and the coarse particles and particulate fractions are sorted out. D ₁₀ of glass A is about 1.6 microns and its D ₉₀ is 10 to 12 microns. The surface area is 1.5 to 1.8 m 2 / g.

Glass B is a barium borosilicate glass used to lower the calcination temperature of the dielectric composite due to the large particle diameter of glass A. The compounding of the glass B is as follows.

Alumina A is a 1 micron powder having a narrow particle size distribution in which D ₁₀ , D ₅₀ and D ₉₀ are 0.5, 1.1 and 2.7 microns, respectively.

This is sorted out and removed by sedimentation. The surface area is about 2.7-2.8 m 2 / g.

Alumina B is a powder of average 0.4 micron particle size with a surface area of about 5 m 2 / g.

The paste composition was prepared by a method known to those skilled in the art of blending thick film materials, and prepared for printing as follows.

The dielectric material was printed to make 1,2 or 3 prints and each print was dried at 80-90 ° C. for 10-15 minutes. The pattern forming layer was then printed using a via fill screen with via openings of some size. Then, the pattern forming paste was dried at 80 to 90 ° C. for 5 to 10 minutes.

Subsequently, with ultrasonic agitation, the overprint layer is impregnated in 1,1,1-trichloroethane until the overprint region is removed and the region under the overprinted pattern forming paste is dissolved away. Formed.

Vias as small as about 0.013 to about 0.018 cm (5 to 7 mils) were resolved with good edge clarity in 85 micron thick dielectric films. This is much better in terms of resolution and thickness than can be achieved with a single patterning step by screen printing.

Example 2

Control of Plasticizer Levels in DP Compositions

In the case where a thicker layer is to be patterned, it is often advantageous to add a plasticizer to the bottom layer to be patterned. A convenient way to determine the optimal level is to create a concentration ladder using different concentrations of plasticizer in the composition to be patterned.

The dielectric paste was prepared by blending as in the method of Example 1 without using a plasticizer. The ladder at the plasticizer level was then adjusted to optimize formulation. The result is as follows.

TABLE 1

The paste was printed and processed as in Example 1 to determine the best operating area. The best area was observed to be 2,5 to 3.5%. It has been found that a film of 40-50 microns in thickness can be sufficiently processed in the compounding region. In the operable areas, relatively high levels of plasticizers lower development time and increase processing capacity.

Example 3

The conductor paste was produced by combining with copper as follows.

Copper Powder, (3-4 Microns) 75.0 Grams

Glass powder C5.0

Polymethylmethacrylate Elbasite 20106.1

t-butylanthraquinone0.6

Shell Ionol0.1

Butyl Carbitol Acetate13.2

Copper pastes were prepared from the above components by methods known to those skilled in the art of thick film paste formulation and prepared for printing.

The film of the conductor composition was printed on the alumina substrate through the 325 mesh screen, and the negative screen print conductor pattern was printed on the upper portion of the copper print using the pattern forming paste of Example 1. All prints were dried at 85-95 ° C. The dried portion was then impregnated in chloroethane and formed the desired pattern by ultrasonic agitation for 15-25 seconds. The part was then fired to form a precise about 0.010 cm (4 mil) line / space pattern. The | plastic | part was | thickness was 10-12 | micron, and the irregularity | about 3mPa / |. The about 0.010 cm (4 mil) line / space resolution was difficult to achieve, although not impossible, to achieve a pattern with 3 m 3 / Ω |. In addition, the structure of about 0.010 cm (4 mil) lines had more precise edge clarity than the screen print portion and flattened the upper surface of the conductor finger. About 0.007 cm (3 mil) lines were resolved when the underprint was applied through a 400 mesh screen to yield a somewhat thin undercoat.

Example 4

A gold conductor composition having conductivity and thickness similar to that of the copper conductor was produced by combining as follows.

Gold Powder75.0 Grams

Copper Bisate1.5

Polymethylmethacrylate3.1

t-butylanthraquinone0.3

Butyl Carbitol Acetate7.2

Shell Ionol0.05

The above components were combined by conventional methods known to those skilled in the thick film method to prepare a gold conductor composition. The gold composition was printed by one application on an alumina substrate through a 32 mesh screen and dried at 85-95 ° C. Subsequently, the pattern forming paste was overprinted with a negative thick film conductor pattern and dried at 85 to 95 ° C.

Example 5

A positive functional conductor paste system was produced by combining in copper as follows.

Copper pastes were prepared from the above components by methods known to those skilled in the art of thick film paste formulation, and prints were prepared.

One film of the conductor composition was printed on an alumina substrate through a 325 mesh screen, and then a negative screen print conductor pattern was printed on top of the copper print using the pattern forming paste of this example. All prints were dried at 85-95 ° C. The dried portion was then impregnated in a 1% potassium carbonate aqueous solution and ultrasonically stirred for 5 to 15 seconds to form the desired pattern. A precise approximately 0.010 cm (4 mil) line / space pattern was formed. The dry portion was 49 microns thick. In addition, about 0.010 cm (4 mil) lines had more precise edge clarity than the screen print portion.

Example 6

Diffusion Patterning by Flexure Printing

The clear resolved print pattern on the flexure plate was transferred to the DP dielectric blend as follows.

A thin film of butyl benzyl phthalate plasticizer was sprayed onto the flexure print plate imaged in a test pattern. This plate was then pressed evenly on the surface of the ceramic portion coated with the dry dielectric composition (see Example 1). The plasticizer transferred from the plate to the dielectric was dried in an oven at 95 ° C. for 5 minutes to diffuse into the dielectric. The phase of the dielectric was developed by impregnation in an ultrasonic bath containing 1,1, 1-trichloroethane chlorotene. The pattern from the plate was clearly visible in the dielectric, thus demonstrating the possibility of other methods of plasticizer precipitation to form diffusion patterned images.

In addition, other image forming methods such as a printing method using an ink jet laser printer or a pattern deposition method using a pen on a plotter can also be used. Rotogravure or offset printing may also be used.

Material system of the selected material

There are several ways to form the thick film pattern using the selective solubilization principle. This pattern can be positive or negative. That is, the area under the overprint may be dissolved as in Examples 1-4, or, for example, the polymer developable with an aqueous solution may be overprinted with an incompatible plasticizer to protect the area immediately below and subsequently to remove the unplasticized material. By removal by water solubilization, it can be insolubilized.

The table below shows a number of acrylic polymer / plasticizer / solvent systems that have been proven to be usable in the process of the present invention.

TABLE 2

The resins can be combined. For example, methyl and ethyl methacrylate can be combined to produce a positive or negative functional resist. In the case of the methyl methacrylate / ethyl methacrylate combination, a plasticizer such as triethylene glycol produces a negative functional resist in a solvent for ethanol pattern formation.

Other resin systems that are not excessively crosslinked, such as polyester, can be patterned in a similar manner. However, it is necessary to determine the solubilizer or insolubilizer and a suitable solvent for pattern formation.

If no solubility envelope is present in the highly crosslinked polymer, the polymer cannot be used in the process.

Epoxy resin:

A positive functional diffusion patterning system with an epoxy resin can be made as follows: Resin in a screen printed inprint film to be prepatterned, for example by condensation polymerization of the sodium salt of bisphenol A with epichlorohydrin. To form. The degree of polymerization of this prepolymer should be at least about 12 units.

Crosslinking amines or polybasic anhydrides such as diethylenetriamine or ethylenediamine or succinic dianhydride are added to the overprint paste. The overprint paste is then printed on the underprint. The composite is then cured to insolubilize the area under the overprinted amine containing paste by insolubilization and the residual material is washed in a suitable solvent such as trichloroethane.

Polyimide:

Negative functional polyimide diffusion patterning systems can be prepared using, for example, incompletely curable systems containing pyromellitic dianhydride (PMDA) and oxydianiline (ODA). Incompletely curable polymers are used as underprints, and pastes containing bases such as triethanolamine or particulate potassium carbonate are overprinted as prints for patterning. The material is then washed in water or about base to remove the area under the overprint.

Other usable materials include benzophenone tetracarboxylic dianhydride reacted with hydroxyethyl methacrylate, and commercially available biferyl dianhydride / paraphenylenediamine systems are also suitable. In the uncured state they are sensitive to negative action phenomena.

Example 7

Diffusion Patterning by Contact Decomposition

The first dielectric thick film paste is blended using polymethyl methacrylate as the binder component of the organic medium, and the upper thick film paste containing ethyl cellulose as the binder component and a small amount of platinum acetyl acetonate acting as a decomposition catalyst is prepared. Blended. This first paste was printed on several alumina substrates through an 80 mesh screen to form a 22 micron thick film (after firing) and a test screen having a via pattern ranging from about 0.013 to about 0.076 cm (5 to 30 mil). The second paste was printed on the first paste. The print layer assembly was then heated for 20 minutes at various temperatures ranging from 240 to 360 ° C., then cooled and each assembly was washed with an aqueous spray. Approximately 0.018 cm (7 mil) vias were resolved. Heat treatments ranging from 280 to 320 ° C. have found that the film surface produces the most uniform vias without corrosion. The composition of this paste is as follows.

TABLE 3

Examples 8 and 9

Aqueous diffusion patterning

Calcium zinc silicate glass was combined with cellulosic vehicle and 3% butyl benzyl phthalate. Each paste film was printed on an alumina substrate and dried at 95-100 ° C. A pattern forming paste containing 7 g of alumina, 3.5 g of tergitol TMN-6, 3.15 g of terpinol isomers and 0.35 g of ethyl cellulose was printed on a dry dielectric paste layer and heated at 95 to 100 ° C. to dry the overprint paste. Tergitol detergent was then diffused into the lower dielectric layer. When the dry layer was washed with tap water, approximately 0.15 cm (6 mil) vias were clearly resolved. A series of tests found that the use of additive plasticizers for the lower polymer layer significantly improved the resolution.

Example 10

In this example, two dielectric pastes were prepared and each was used to produce a series of pattern forming systems on an alumina substrate using the same pattern forming paste. The compositions of the three dielectric pastes were different, dielectric paste B contained butyl benzyl phthalate and dielectric paste A containing a highly volatile dip phthalate plasticizer.

The composition of dielectric paste A was the same as that of Example 7, except that dipropyl phthalate, which is more volatile as a plasticizer, was used instead of dibutyl benzol phthalate. The composition of the pattern forming paste was the same as that in Example 7, except that platinum acetylacetate was not contained.

All of the dielectric paste was printed through a screen with openings of about 0.015 to about 0.028 cm (6 to 11 mils) and dried at 80 to 85 ° C. for 12 minutes. The pattern forming paste was then printed on the dry dielectric layer, heated to 95-100 ° C. for 10 minutes to dry the layer and to spread the plasticizer into the lower dielectric layer. The assembly was then developed for 10-15 seconds with a chlorotene spray, washed with water and then dried with an air knife. In measuring the vias created in each assembly, the vias from the dielectric layer containing the more volatile plasticizer were found to be approximately the same size as the openings of the frit screen used to apply the pattern forming layer uniformly.

TABLE 4

Term Solving

Carbitol

Trademark for diethylene glycol ethyl ether from Union Carbide Corporation (Danbury, Connecticut).

Carboset

ratio. F. Trademark for methylmethacrylate copolymers from B. F. Goodrich Co., Cleveland, Ohio.

Elvacite 2010

this. children. Trademark for methacrylate resins of E. I. du Pont de Nemours and Co., Wilmington, Delaware.

Plane MF and TF (Freeon MF, TF)

this. children. Respective trademarks of Trichlorofluoromethane and Trichlorofluoroethane from Duupan de Nemoa & Company, Wilmington, Delaware.

Ionol

Trademark for Hazardous Type Phenolic Antioxidants from Shell Chemical Co., Houston, Texas.

Santicizer

Trademark for N-alkyl-para-toluene sulfonamide plasticizers from Monsanto Chemical Co. (St. Louis, MO).

T-200

Hercules, Inc. Trademark for ethylcellulose from Hercules, Inc., Wilmington, Delaware.

Tergitol

Trademark for nonionic surfactants from Union Carbide Corporation, New York, NY.

Claims (12)

a. Applying an unpatterned first layer comprising a solid organic polymer capable of dispersing in a predetermined eluent to the substrate, b. Applying to the unpatterned first layer a patterned second layer comprising a formulation capable of varying the dispersibility of the solid organic polymer in a predetermined eluent, c. Patterning diffusion of the dispersing modifier into the underlying solid organic polymer layer, and d. A non-photographic method of forming a pattern in an organic polymer film, comprising a continuous step of washing and removing an area of a lower first layer that can be dispersed in an eluent with a predetermined eluent. a. Applying an unpatterned first solid organic polymer layer consisting of a solid organic polymer to a substrate, b. A solid organic polymer in the unpatterned first phase organic polymer layer, (1) a dispersant for the polymer of the first organic polymer layer, and (2) a dispersibility modifier having an atmospheric boiling point higher than the solvent and optionally a viscous dispersion of the solvent. Applying a patterned second layer consisting of: c. Drying the patterned second layer to remove solvent therefrom and patterning diffusion of the solubilizer into the lower first organic polymer layer, and d. An organic polymer film comprising a continuous step of washing and removing the diffusion patterned region of the patterned second layer and the lower first layer in an eluent that can be dispersed by the second layer and the first layer. Negative functional non-photographic method of forming a pattern. a. Applying to the substrate an unpatterned first layer consisting of a solid organic polymer that can be dispersed in a predetermined solvent, b. Applying to the unpatterned first layer a patterned second layer consisting of an insolubilizer capable of reducing the solubility of the organic polymer in a solvent, c. Heating the patterned second layer to patternically diffuse the insolubilizer into the lower first organic polymer layer and impart insolubility in the solvent to the diffusion patterning region of the polymer in the first layer, and d. A positive functional non-photographic method of forming a pattern in an organic polymer film, consisting of a continuous step of washing and removing the unpatterned region of the lower first layer in a predetermined solvent. The process of claim 1 wherein the dispersibility modifier is a catalyst for decomposition of the first layer polymer. The method of claim 1 wherein the dispersibility modifier is a plasticizer for the first layer polymer. The method of claim 1 wherein the dispersibility modifier is a detergent capable of dispersing the first layer polymer. a. Applying to the substrate an unpatterned first layer consisting of a soluble solid organic polymer in a predetermined solvent, b. Applying to the unpatterned first layer a patterned second layer comprising a formulation capable of varying the solubility of the solid organic polymer in a predetermined solvent, c. Patterning diffusion of the solubility modifier into the lower solid organic polymer layer, and d. A non-photographic method of forming a pattern on an organic polymer film, comprising a continuous step of washing and removing a region of the lower first layer that is soluble in a solvent with a predetermined solvent. a. Applying an unpatterned first solid organic polymer layer consisting of a solid organic polymer to a substrate, b. A patterned second composed of a solid organic polymer in the unpatterned first solid organic polymer layer, (1) a solubilizer in the polymer of the first organic polymer layer and (2) an atmospheric boiling point higher than the solvent and a viscous solution of the solvent Applying a layer, c. Drying the patterned second layer to remove solvent therefrom and patterning diffusion of the solubilizer into the lower first organic polymer layer, and d. An organic polymer comprising a continuous step of washing and removing the diffusion patterned region of the patterned second layer and the lower first layer in a second solvent that can be dissolved by the second pattern and the diffusion patterned region of the first layer Negative functional non-photographic method of forming a pattern on a film. a. Applying an unpatterned first layer consisting of a soluble solid organic heavy body in a predetermined solvent to the substrate, b. Applying to the unpatterned first layer a patterned second layer consisting of an insolubilizer capable of reducing the solubility of the organic polymer in a solvent. c. Heating the patterned second layer to patternically diffuse the insolubilizer into the lower first organic polymer layer and impart insolubility in the solvent to the diffusion patterning region of the polymer in the first layer, and d. A positive functional non-photographic method of forming a pattern in an organic polymer film, consisting of a continuous step of washing and removing the unpatterned region of the lower first layer in a predetermined solvent. a. Applying to the substrate an unpatterned thick film layer of electrically functional particulate solid dispersed in an organic medium consisting of a first solid polymer dissolved in a volatile solvent, b. Removing the solvent from the thick film layer by evaporation, c. A non-solvent unpatterned thick film layer is coated with an amorphous polymer, a patterned second layer comprising a viscous dispersion of a first solvent plasticizer and a second solvent that is soluble in the first layer polymer and having a higher boiling point than the second solvent. Step d. Heating the patterned second layer to simultaneously remove the second solvent therefrom, and patterning diffusion of the plasticizer from the second layer to the lower region of the first layer, and e. Thick layer, consisting of a continuous step of washing the layers with a solvent that can dissolve both the plasticizing first polymer and the second layer polymer, thereby simultaneously removing the patterned second layer and the underlying diffusion patterned regions of the first layer. A non-photographic method of forming a pattern on. The method of claim 10, wherein the first layer composite and the patterned layer polymer are polymers of the same composition. The method of claim 10 wherein the first layer polymer is poly (methacrylate), the plasticizer is alkylphthalate, and the volatile solvent in the patterned layer is terpineol.